Ru-Ni/Al<sub>2</sub>O<sub>3</sub>催化马来酸二甲酯加氢性能研究

王磊; 庆绍军; 赵显梅; 唐亚昆; 刘浪; 高志贤

Ru-Ni/Al₂O₃催化马来酸二甲酯加氢性能研究

王磊^{1, 2},
庆绍军³,
赵显梅^{1, 2},
唐亚昆^{1, 2},
刘浪^{1, 2, ,},
高志贤³

1.
新疆大学化学化工学院, 新疆乌鲁木齐 830046
2.
新疆大学应用化学研究所能源材料化学教育部重点实验室, 新疆乌鲁木齐 830046
3.
中国科学院山西煤炭化学研究所, 山西太原 030001

详细信息

中图分类号: O643.38
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- 被引次数: 0
出版历程
- 收稿日期: 2017-05-17
- 修回日期: 2017-10-10
- 网络出版日期: 2021-01-23
- 刊出日期: 2018-02-10

Study on the catalytic hydrogenation of dimethyl maleate over Ru-Ni/Al₂O₃

WANG Lei^{1, 2},
QING Shao-jun³,
ZHAO Xian-mei^{1, 2},
TANG Ya-kun^{1, 2},
LIU Lang^{1, 2
, ,},
GAO Zhi-xian³

1.
School of Chemistry and Chemical Engineering, Xinjiang University, Urumqi 830046, China
2.
Key Laboratory of Energy Materials Chemistry, Ministry of Education, Institute of Applied Chemistry, Xinjiang University, Urumqi 830046, China
3.
Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China

More Information

Corresponding author: LIU Lang, Tel:0991-8588883, E-mail:liulang@xju.edu.cn, llyhs1973@sina.com

摘要

摘要: 以Al₂O₃为载体, RuCl₃·xH₂O及Ni(NO₃)₂·6H₂O为活性组分前驱体, 采用吸附-沉淀法制备系列Ru-Ni/Al₂O₃催化剂, 以马来酸二甲酯(DMS)催化加氢为探针反应, 考察了活化条件和Ni的添加量对催化剂性能的影响。随Ni负载量的升高, Ru-Ni/Al₂O₃催化剂活性呈现先升高后降低的趋势, 在Ni：Ru的原子比为6：1时(催化剂Ru₁Ni₆/Al)催化活性最高。催化剂Ru₁Ni₆/Al在氢气中200 ℃直接还原后的平均转化率与氢气中400 ℃还原后的平均转化率接近, 达到了单组分Ru/Al催化剂的1.5倍以上。XPS、XRD、H₂-TPR数据表明, Ru与Ni之间发生了较强的相互作用, Ni的加入促进了金属Ru在载体上的分散, 提高了催化活性。
- Ru-Ni/Al₂O₃ /
- 催化加氢 /
- 马来酸二甲酯 /
- 丁二酸二甲酯
Abstract: A series of Ru-Ni/Al₂O₃ catalysts were prepared via adsorption-precipitation method, using Al₂O₃ as the support and RuCl₃·xH₂O and Ni(NO₃)₂·6H₂O as precursors.Effects of pretreatment conditions and the amount of Ni on the catalytic behaviors of the catalysts were investigated.The catalytic activities of Ni-modified Ru catalysts increased with the increase of the Ni content firstly and then decreased.The highest hydrogenation activity was obtained as the atomic ratio of Ni:Ru is 6:1.The catalytic activity of Ru₁Ni₆/Al-fresh subjected to reduction at 200℃ has no significant difference with the sample reduced at 400℃, reaching to 1.5 times that of Ru/Al₂O₃ with the same pretreatment.Based on the results of XPS, XRD and H₂-TPR, the reason for the promoted catalytic effect of Ni was disclosed.It was found that the dispersion of Ru could be improved as the promotion of Ni, resulting in the improvement of the catalytic performance of the Ru catalyst.
- Ru-Ni/Al₂O₃ /
- catalytic hydrogenation /
- dimethyl maleate /
- dimethyl succinate

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图 1 新鲜催化剂的H₂-TPR谱图

a:Ru/Al-fresh; b:Ru₁Ni₁/Al-fresh; c:Ru₁Ni₂/Al-fresh;
d:Ru₁Ni₄/Al-fresh; e:Ru₁Ni₆/Al-fresh;
f:Ru₁Ni₈/Al-fresh; g:Ni/Al-fresh

Figure 1 H₂-TPR profiles of the fresh samples

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图 2 催化剂Ru_xNi_y/Al-H1的XRD谱图

a:Ru/Al-H1;b:Ru₁Ni₁/Al-H1;c:Ru₁Ni₂/Al-H1;
d:Ru₁Ni₄/Al-H1;e:Ru₁Ni₆/Al-H1;
f:Ru₁Ni₈/Al-H1;g:Ni/Al-H1

Figure 2 XRD patterns of Ru_xNi_y/Al-H1

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图 3 催化剂Ru/Al-H1、Ru₁Ni₆/Al-H1、Ru₁Ni₈/Al-H1及Ni/Al-H1的XPS谱图

Figure 3 XPS spectra of Ru/Al-H1, Ru₁Ni₆/Al-H1, Ru₁Ni₈/Al-H1 and Ni/Al-H1catalysts

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图 4 催化剂Ru_xNi_y/Al-H1上马来酸二甲酯的加氢活性

Figure 4 Catalytic performances of Ru_xNi_y/Al-H1 for hydrogenation of DMM reaction conditions:pressure 1.0 MPa, temperature 70 ℃, Cat.200 mg, MeOH 90 mL

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图 5 不同预处理条件下样品的H₂-TPR谱图

a:Ru/Al-fresh; b:Ru₁Ni₆/Al-fresh; c:Ni/Al-fresh;
d:Ru₁Ni₆/Al-H; e:Ru₁Ni₆/Al-H(after reaction)

Figure 5 H₂-TPR profiles of the samples with varied pretreatments

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图 6 不同预处理所得催化剂上马来酸二甲酯的加氢活性

Figure 6 Catalytic performances for hydrogenation of DMM over the samples with varied pretreatments reaction conditions:pressure 1.0 MPa, temperature 70 ℃, Cat.200 mg, MeOH 90 mL

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表 1 催化剂编号与预处理条件

Table 1 Catalyst codes and pretreatment conditions

Catalyst code	Pretreatment procedure
Ru/Al-fresh	without pretreatment
Ru₁Ni₁/Al-fresh	without pretreatment
Ru₁Ni₂/Al-fresh	without pretreatment
Ru₁Ni₄/Al-fresh	without pretreatment
Ru₁Ni₆/Al-fresh	without pretreatment
Ru₁Ni₈/Al-fresh	without pretreatment
Ni/Al-fresh	without pretreatment
Ru/Al-H	Ru/Al-fresh reduced at 200 ℃ for 2 h in H₂
Ru₁Ni₆/Al-H	Ru₁Ni₆/Al-fresh reduced at 200 ℃ for 2 h in H₂
Ru/Al-H1	Ru/Al-fresh reduced at 400 ℃ for 2 h in H₂
Ru₁Ni₁/Al-H1	Ru₁Ni₁/Al-fresh reduced at 400 ℃ for 2 h in H₂
Ru₁Ni₂/Al-H1	Ru₁Ni₂/Al-fresh reduced at 400 ℃ for 2 h in H₂
Ru₁Ni₄/Al-H1	Ru₁Ni₄/Al-fresh reduced at 400 ℃ for 2 h in H₂
Ru₁Ni₆/Al-H1	Ru₁Ni₆/Al-fresh reduced at 400 ℃ for 2 h in H₂
Ru₁Ni₈/Al-H1	Ru₁Ni₈/Al-fresh reduced at 400 ℃ for 2 h in H₂
Ni/Al-H1	Ni/Al-fresh reduced at 400 ℃ for 2 h in H₂

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表 2 还原活化催化剂上Ru/Al与Ni/Al的原子比

Table 2 Ru/Al and Ni/Al atomic ratios of the reduced catalysts

Catalyst code	Ru/Al-H1	Ru₁Ni₆/Al-H1	Ni/Al-H1
Ru/Al (atomic ratio)	0.10	0.15	-
Ni/Al (atomic ratio)	-	0.88	0.10

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